US11866519B2 - Cellulose-containing materials - Google Patents
Cellulose-containing materials Download PDFInfo
- Publication number
- US11866519B2 US11866519B2 US17/276,089 US201917276089A US11866519B2 US 11866519 B2 US11866519 B2 US 11866519B2 US 201917276089 A US201917276089 A US 201917276089A US 11866519 B2 US11866519 B2 US 11866519B2
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- US
- United States
- Prior art keywords
- cellulose
- solution
- solid material
- protein
- source
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 329
- 239000001913 cellulose Substances 0.000 title claims abstract description 329
- 239000000463 material Substances 0.000 title claims abstract description 152
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 225
- 239000011343 solid material Substances 0.000 claims abstract description 167
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 161
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 161
- 239000002904 solvent Substances 0.000 claims abstract description 121
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 111
- 235000019253 formic acid Nutrition 0.000 claims abstract description 111
- 238000000034 method Methods 0.000 claims abstract description 104
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 83
- 108010076876 Keratins Proteins 0.000 claims description 48
- 102000011782 Keratins Human genes 0.000 claims description 48
- 238000005345 coagulation Methods 0.000 claims description 48
- 230000015271 coagulation Effects 0.000 claims description 48
- 210000002268 wool Anatomy 0.000 claims description 34
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 claims description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- 229920000742 Cotton Polymers 0.000 claims description 23
- 238000007710 freezing Methods 0.000 claims description 20
- 230000008014 freezing Effects 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 239000000835 fiber Substances 0.000 claims description 18
- 239000003205 fragrance Substances 0.000 claims description 14
- 229920001131 Pulp (paper) Polymers 0.000 claims description 13
- 239000000049 pigment Substances 0.000 claims description 9
- 238000010257 thawing Methods 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001112 coagulating effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 220
- 235000018102 proteins Nutrition 0.000 description 153
- 239000002244 precipitate Substances 0.000 description 41
- 150000004675 formic acid derivatives Chemical class 0.000 description 35
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 31
- 229940044170 formate Drugs 0.000 description 30
- 238000001125 extrusion Methods 0.000 description 24
- 241000219146 Gossypium Species 0.000 description 22
- 241000196324 Embryophyta Species 0.000 description 21
- 239000012266 salt solution Substances 0.000 description 21
- -1 zinc halides Chemical class 0.000 description 19
- 108010076119 Caseins Proteins 0.000 description 18
- 239000005018 casein Substances 0.000 description 18
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 18
- 235000021240 caseins Nutrition 0.000 description 18
- 238000004090 dissolution Methods 0.000 description 18
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 18
- 239000011701 zinc Substances 0.000 description 17
- 229910052725 zinc Inorganic materials 0.000 description 17
- 229920003043 Cellulose fiber Polymers 0.000 description 14
- 239000004753 textile Substances 0.000 description 14
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 13
- 235000018417 cysteine Nutrition 0.000 description 13
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 238000006467 substitution reaction Methods 0.000 description 11
- 238000002166 wet spinning Methods 0.000 description 11
- 108010022355 Fibroins Proteins 0.000 description 10
- 241000220317 Rosa Species 0.000 description 10
- 239000011592 zinc chloride Substances 0.000 description 9
- 235000005074 zinc chloride Nutrition 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 7
- 239000004280 Sodium formate Substances 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 235000019254 sodium formate Nutrition 0.000 description 6
- 229940102001 zinc bromide Drugs 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 210000003746 feather Anatomy 0.000 description 5
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920005615 natural polymer Polymers 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 239000000109 continuous material Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000001212 derivatisation Methods 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 102000034240 fibrous proteins Human genes 0.000 description 4
- 108091005899 fibrous proteins Proteins 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 4
- 210000000003 hoof Anatomy 0.000 description 4
- 210000003284 horn Anatomy 0.000 description 4
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229960003067 cystine Drugs 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000022244 formylation Effects 0.000 description 2
- 238000006170 formylation reaction Methods 0.000 description 2
- 210000004209 hair Anatomy 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000011492 sheep wool Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000003313 weakening effect Effects 0.000 description 2
- 239000012991 xanthate Substances 0.000 description 2
- AJWXULAAWUPOJS-UHFFFAOYSA-L zinc;diformate;dihydrate Chemical compound O.O.[Zn+2].[O-]C=O.[O-]C=O AJWXULAAWUPOJS-UHFFFAOYSA-L 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- 241000282832 Camelidae Species 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 240000000047 Gossypium barbadense Species 0.000 description 1
- 235000009429 Gossypium barbadense Nutrition 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- 125000000151 cysteine group Chemical group N[C@@H](CS)C(=O)* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000009944 hand knitting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- 230000031787 nutrient reservoir activity Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 102000034272 protein filaments Human genes 0.000 description 1
- 108091005974 protein filaments Proteins 0.000 description 1
- 239000012460 protein solution Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/04—Cellulose formate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/003—Pulping cellulose-containing materials with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/22—Post-esterification treatments, including purification
- C08B3/26—Isolation of the cellulose ester
- C08B3/28—Isolation of the cellulose ester by precipitation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
- C08H1/06—Macromolecular products derived from proteins derived from horn, hoofs, hair, skin or leather
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H99/00—Subject matter not provided for in other groups of this subclass, e.g. flours, kernels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
- C08L89/04—Products derived from waste materials, e.g. horn, hoof or hair
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
- D01F2/30—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate by the dry spinning process
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
- C08J2389/04—Products derived from waste materials, e.g. horn, hoof or hair
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
Definitions
- the present invention relates to a process for solubilising cellulose and coagulating the resulting solution to form a cellulose-containing material.
- the process can further comprise solubilising protein and coagulating the resulting solution to form a cellulose/protein-containing material.
- Natural fibres such as cotton, wool and silk have many desirable properties in textile and other applications, including sustainability due to their natural origin, their interaction with moisture and the resulting comfort next to the skin. Their use in textile applications is widespread. Natural fibres have limitations, including their fibre diameter, which is a key determinant of softness and results from the natural fibre formation process, as does their staple length. In addition, the surface structure of some fibres, such as wool, is not smooth and this may create problems during fibre processing and use.
- Fibres can be made through extrusion processes, such as wet spinning or melt spinning. Such fibres are typically continuous filament, with a controllable diameter and with a smooth or controllable surface topography. Extrusion processes may, therefore, overcome several of the limitations of natural fibres.
- Derivatisation to create cellulose acetate also provides materials that are extrudable through wet spinning or solvent spinning systems, and such materials are commonly use in the creation of textile fibres. Unlike cellulose acetate, however, the previous use of cellulose formate has been limited due to the instability of the material and its susceptibility to degradation.
- the use of zinc salts in the presence of formic acid to dissolve cellulose is known in the art (CN 105153316 and US 2014/0090640), however, these approaches leave the cellulose susceptible to hydrolysis and dissolution under acidic conditions. This leads to loss of degree of polymerisation and weakening of any subsequently reconstituted materials.
- Cellulose formate derivatives have been prepared using formic acid and zinc halides under concentrated conditions that may avoid hydrolysis (GB 260650 and GB 275641). Other processes for preparing cellulose formate have relied on additional phosphoric acid to achieve the reaction conditions favourable for formylation (U.S. Pat. No. 4,839,113).
- Such derivatisation may use reduction (GB 690566), sulfitolysis (U.S. Pat. No. 7,465,321) or alkali treatment (WO 2013/043062) to create an extrudable liquid.
- the present invention provides a process for producing a cellulose-containing material comprising:
- the present invention provides a process for producing a cellulose-containing material comprising:
- the present invention provides a process for producing a cellulose-containing material comprising:
- the cellulose source comprises cellulose with a degree of polymerisation of at least about 1000. In another embodiment, the cellulose source comprises cellulose with a degree of polymerisation of at least about 1200. In another embodiment, the cellulose source comprises cellulose with a degree of polymerisation of up to about 5000.
- the cellulose source comprises cotton. In another embodiment, the cellulose source comprises wood pulp.
- the cellulose source may comprise a plant part.
- the plant part is a leaf or petal.
- the cellulose source may comprise a mixture of two or more cellulose sources.
- the solvent comprises less than about 10% w/w water. In another embodiment, the solvent comprises less than about 5% w/w water. In another embodiment, the solvent comprises less than about 2% w/w water. In another embodiment, the solvent comprises less than about 1% w/w water.
- the solvent comprises a solution of zinc formate and formic acid.
- the concentration of zinc formate is about 20% w/v to about 40% w/v and, in another embodiment, the concentration of zinc formate is about 40% w/v.
- the process may further comprise producing the solution of zinc formate and formic acid from a zinc halide and formic acid.
- the zinc halide may be selected from zinc chloride, zinc bromide or a mixture thereof.
- the concentration of zinc halide is about 10% w/v to about 50% w/v.
- the concentration of zinc halide is about 20% w/v to about 45% w/v.
- the concentration of zinc halide is about 40% w/v and, in another embodiment, the concentration of zinc halide is about 25% w/v.
- the cellulose source and solvent may be contacted for about 4 hours to about 9 hours, or for about 9 hours.
- the cellulose source and solvent may be contacted at a temperature of about 15° C. to about 30° C.
- the coagulation bath comprises water. In another embodiment, the coagulation bath consists essentially of water.
- the temperature of the coagulation bath may be about 5° C. to about 15° C.
- the solid material provided in (b) comprises a fibre or film.
- the oxidising solution comprises aqueous hydrogen peroxide. In one embodiment, the oxidising solution comprises about 0.5% w/w to about 5.0% w/w hydrogen peroxide in water and, in another embodiment, about 0.5% w/w to about 1.0% w/w hydrogen peroxide in water and, in another embodiment, about 0.7% w/w hydrogen peroxide in water.
- the solid material may be immersed in the oxidising solution for about 1 minute to about 5 minutes. In one embodiment, the solid material is immersed in the oxidising solution at a temperature of about 5° C. to about 15° C.
- step (e) comprises freeze drying the solid material from (d) to provide the cellulose-containing material.
- step (e) comprises thawing the frozen solution from (d), removing the solid material from the thawed solution, and drying the solid material to provide the cellulose-containing material.
- step (e) comprises thawing the frozen water from (d), removing the solid material from the thawed water, and drying the solid material to provide the cellulose-containing material.
- the frozen solution or water is thawed at a temperature of about 5° C. to about 30° C.
- the formate salt in step (c) is selected from sodium formate, potassium formate, ammonium formate or a mixture of any two or more thereof.
- the aqueous formate salt solution in step (c) is an aqueous solution of sodium formate.
- the concentration of formate salt in the aqueous formate salt solution in step (c) is between about 20% w/v and about 60% w/v.
- step (d) comprises drying the solid material from (c) to form a residue of solid formate salt on the surface of the solid material, then rinsing and drying the solid material to provide the cellulose-containing material.
- the cellulose-containing material provided in (e) of the first or second aspect or (d) of the third aspect may comprise a fibre or film.
- step (a) further comprises contacting a protein source with the solvent.
- the protein source may be contacted with the solvent simultaneously or sequentially with the cellulose source.
- the protein source may comprise keratin.
- the protein source may comprise wool.
- the protein source comprises casein.
- the protein source comprises fibroin.
- the protein source may comprise silk.
- the protein source is formylated.
- the solvent further comprises cysteine.
- the solvent may comprise about 10% w/v to about 70% w/v cysteine, or about 50% w/v cysteine.
- the process further comprises:
- the formic acid comprises less than about 2% w/w water.
- the cellulose-containing material comprises one or more pigments from the cellulose source.
- the cellulose-containing material may additionally or alternatively comprise one or more fragrances from the cellulose source.
- the cellulose-containing material further contains protein.
- the present invention provides a process for producing a cellulose/protein-containing material comprising:
- the present invention provides a process for producing a cellulose/protein-containing material comprising:
- the present invention provides a process for producing a cellulose/protein-containing material comprising:
- the protein source comprises keratin.
- the protein source may comprise wool.
- the protein source comprises casein.
- the protein source comprises fibroin.
- the protein source may comprise silk.
- the present invention provides a process for producing a cellulose/protein-containing material comprising:
- the present invention provides a process for producing a cellulose/protein-containing material comprising:
- the present invention provides a process for producing a cellulose/protein-containing material comprising:
- the protein source comprises keratin formate.
- the present invention provides a process for producing a cellulose/protein-containing material comprising:
- the present invention provides a process for producing a cellulose/protein-containing material comprising:
- the present invention provides a process for producing a cellulose/protein-containing material comprising:
- the protein source comprises keratin.
- the present invention also provides a material produced by a process of the invention.
- the present invention provides an extruded material comprising cellulose and protein. In another aspect, the present invention provides a substantially continuous material comprising cellulose and protein.
- the material consists essentially of cellulose and protein. In another embodiment, the material consists of cellulose and protein.
- the material may be a fibre or a film.
- the material has a protein content of about 5% w/w or more.
- the protein may comprise keratin.
- the keratin may be derived from wool.
- the cellulose may be derived from cotton, wood pulp, plant parts or a mixture of any two or more thereof.
- the material comprises one or more pigments and/or one or more fragrances from the plant parts.
- the present invention provides an extruded material comprising cellulose and one or more pigments and/or fragrance from plant parts. In another aspect, the present invention provides a substantially continuous material comprising cellulose and one or more pigments and/or one or more fragrances from plant parts.
- % w/v as used in this in this specification means the weight in grams of a solute per 100 ml of a solution.
- the present invention broadly relates to a process for producing cellulose-containing materials by solubilising cellulose from a cellulose source then processing the resulting solution to produce, for example, reconstituted cellulose fibres and films.
- the process can also further comprise solubilising protein and processing the resulting solution to produce, for example, reconstituted cellulose/protein fibres and films.
- Extrusion of the resulting formic acid solutions into a coagulation bath generates products comprising the polymer materials.
- wet spinning can be used to generate the materials as fibres.
- a cellulose source and a protein source may be solubilised in the same solution, or in separate solutions that are then combined prior to extrusion.
- the initial product of the extrusion comprises, for example, cellulose formate or cellulose/keratin formate, when the protein source comprises keratin.
- Cellulose formate is an unstable material, but the inventor has determined that, for example, the use of oxidants and low temperature processing, or other process steps as described herein, can stabilise the extruded material and generate cellulose and cellulose/protein fibres that are suitable for textile processing.
- the present invention relates to a process for producing a cellulose-containing material comprising contacting a cellulose source with a solvent comprising zinc ions and formic acid to provide a solution, extruding the solution into a coagulation bath to provide a solid material, treating the solid material, and isolating the solid material after treatment, to provide the cellulose-containing material.
- the present invention also relates to a process for producing a cellulose-containing material comprising:
- one aspect of the present invention relates to a process for producing a cellulose-containing material comprising:
- the solvent comprises zinc ions and formic acid.
- the solvent comprises a solution of zinc formate in formic acid.
- the concentration of zinc formate may be about 20% w/v to about 40% w/v. It may be difficult to dissolve a cellulose source in solutions having significantly lower or higher concentrations of zinc formate. In one embodiment, the concentration of zinc formate is about 40% w/v.
- the solvent may be prepared by dissolving zinc formate in formic acid.
- the zinc formate comprises less than about 5% w/w water, more preferably less than about 2% w/w water. More preferably, the zinc formate is substantially anhydrous.
- the formic acid is at least 90% w/w formic acid. More preferably, the formic acid is about 95% w/w formic acid, more preferably about 98% w/w formic acid. Formic acid is commercially available in such concentrations.
- the solvent comprises a concentration of anhydrous zinc formate of about 20% w/v to about 40% w/v in 98% formic acid.
- minimising the amount of water in the solvent has been found to improve the solubility of the cellulose source material in the solvent.
- the solvent typically comprises less than about 10% w/w water. Preferably, the solvent comprises less than about 5% w/w water. More preferably, the solvent comprises less than about 2% w/w water. In one embodiment, the solvent comprises less than about 1% w/w water.
- the solubility of cellulose in the solvent typically increases with as the water content of the solvent decreases.
- Zinc formate may be prepared by reacting a zinc halide, including zinc chloride, zinc bromide or a mixture thereof, with concentrated formic acid.
- the resulting zinc formate can be isolated, typically as a powder, and dried to provide anhydrous zinc formate.
- the zinc formate may then be dissolved in formic acid to provide the solvent comprising zinc ions and formic acid.
- the solvent comprising zinc ions and formic acid may be produced in situ by reacting the zinc halide with concentrated formic acid and without isolating zinc formate.
- the concentration of zinc halide in the formic acid is typically about 10% w/v to about 50% w/v.
- the concentration of zinc halide is about 20% w/v to about 50% w/v. More preferably, the concentration of zinc halide is about 20% w/v to about 45% w/v. In one embodiment, the concentration of zinc halide is about 40% w/v. In another embodiment, the concentration of zinc halide is about 25% w/v.
- the zinc halide comprises less than about 5% w/w water, more preferably less than about 2% w/w water. More preferably, the zinc halide is substantially anhydrous.
- the solvent comprises a concentration of anhydrous zinc chloride of about 20% w/v to about 50% w/v in 98% formic acid
- the solvent is contacted with a cellulose source to provide a solution.
- the cellulose source dissolves.
- a variety of cellulose sources are suitable for use in the invention. For example, native cellulose sources having a relatively low degree of polymerisation, but also cellulose sources having a relatively high degree of polymerisation (DP).
- Low DP cellulose sources having a DP of up to about 1000 or about 800-1200, such as wood pulp, are readily dissolved in the solvent of the invention.
- Wood pulp can also be dissolved in other common solvent systems, such as those using xanthate, cuprammonium complex or N-methylmorpholine N-oxide. But dissolution of higher DP cellulose sources is generally not possible in these solvent systems.
- Cotton linter typically has a DP of about 1000-2000 and cotton may have a DP of about 1500-5000 or higher.
- the zinc ion/formic acid solvent of the invention has been found to dissolve relatively high DP cellulose sources, for example cellulose sources having a DP of up to about 5000, such as cotton (including Egyptian cotton). In one embodiment, the solvent of the invention dissolves about 2% w/v cotton.
- the cellulose source comprises cellulose with a DP of at least about 1000. In another embodiment, the cellulose source comprises cellulose with a DP of at least about 1200.
- the cellulose source may comprise a mixture of two or more cellulose sources, each of which has the same or a different DP.
- the cellulose source may comprise a mixture of two or more of cotton, wood pulp and plant parts.
- the cellulose source comprises a mixture of cotton and wood pulp.
- the cellulose source comprises a mixture of cotton and plant parts.
- the cellulose source comprises a mixture of wood pulp and plant parts.
- the cellulose source comprises a mixture of cotton, wood pulp and plant parts.
- the solvent of the present invention may be used to solubilise cellulose from whole and/or unprocessed plant parts, such as leaves, petals and fruit skins.
- Preferred plant parts include leaves and petals.
- Such plant parts typically contain additional components, such as hemi-cellulose, pectin and other non-structural polysaccharides, which interfere with the xanthate or cuprammonium processes used in rayon processing and render them ineffective.
- plant parts may be dissolved using the solvent of the present invention.
- cellulose-containing materials produced by the process of the present invention can retain the colour and/or fragrance features of the cellulose source.
- fibres that are rose coloured and have a rose fragrance can be produced using rose petals as the cellulose source.
- fibres that are green or brown can be produced using the same coloured leaves as the cellulose source.
- the cellulose-containing material may comprise one or more pigments from the cellulose source.
- the cellulose-containing material may comprise one or more fragrances from the cellulose source.
- the solvent of the invention generates cellulose formate with a low degree of substitution, generally 2 or less, and may generate cellulose formate with a degree of substitution of 1 or less. While cellulose formate with a high degree of substitution has a high solubility in a range of solvent systems, including concentrated formic acid, DMF and DMSO, previous approaches to using cellulose formate with a low degree of substitution, for example 2 or less or 1 or less, have typically not provided solutions with a high enough concentration (sufficient solubility of cellulose) to allow wet spinning.
- the solvent system of the invention provides cellulose formate with a low degree of substitution, and is able to produce solutions with a sufficiently high concentration of cellulose for subsequent wet spinning of fibres.
- the solvent of the invention dissolves up to about 5% w/v cellulose in a solvent comprising 98% formic acid.
- the solvent of the invention dissolves up to about 4% w/v cellulose in a solvent comprising 98% formic acid.
- the solvent of the invention dissolves up to about 3.5% w/v cellulose in a solvent comprising 98% formic acid.
- the solvent of the invention dissolves up to about 3% w/v cellulose in a solvent comprising 98% formic acid.
- the solvent of the invention dissolves up to about 2.5% w/v cellulose in a solvent comprising 98% formic acid. In another embodiment, the solvent of the invention dissolves up to about 2.3% w/v cellulose in a solvent comprising 98% formic acid. In another embodiment, the solvent of the invention dissolves up to about 2% w/v cellulose in a solvent comprising 98% formic acid.
- the cellulose source and the solvent are typically contacted for a time sufficient to dissolve the cellulose.
- the cellulose source may conveniently be contacted by immersing it into the solvent.
- the invention is not limited thereto and other suitable methods will be apparent to those persons skilled in the art.
- the contacting time may depend on the DP of the cellulose in the cellulose source. In one embodiment, the contacting time is about 4 hours to about 9 hours. Contacting times outside this range may, however, still be useful. For example, a contacting time of about 4 hours may be sufficient to dissolve cellulose having a relatively low DP, while a contacting time of about 9 hours may be required to dissolve cellulose having a relatively high DP.
- the mixture of cellulose source and solvent is agitated, stirred or otherwise mixed during contacting.
- the agitation, stirring or mixing may be continuous or discontinuous during the contacting.
- the amount of cellulose source is up to about 5% w/v of solvent. In another embodiment, the amount of cellulose source is up to about 4% w/v of solvent. In another embodiment, the amount of cellulose source is up to about 3.5% w/v of solvent. In another embodiment, the amount of cellulose source is up to about 3% w/v of solvent. In another embodiment, the amount of cellulose source is up to about 2.5% w/v of solvent. In another embodiment, the amount of cellulose source is up to about 2.3% w/v of solvent. In another embodiment, the amount of cellulose source is up to about 2% w/v of solvent.
- the temperature at which the contacting step is performed may be, for example, about 15° C. to about 30° C. Temperatures outside this range may, however, still be useful.
- the contacting step may be performed at ambient (room) temperature, typically about 20° C. to about 25° C.
- the resulting solution may comprise up to about 5% w/v cellulose. Accordingly, in one embodiment, the solution comprises about 5% w/v cellulose. In another embodiment, the solution comprises about 4% w/v cellulose. In another embodiment, the solution comprises about 3.5% w/v cellulose. In another embodiment, the solution comprises about 3% w/v cellulose. In another embodiment, the solution comprises about 2.5% w/v cellulose. In another embodiment, the solution comprises about 2.3% w/v cellulose. In another embodiment, the solution comprises about 2% w/v cellulose.
- keratin derived from wool or other sources such feathers, horns and hooves
- extruded fibres typically with chemical modification to create a derivative suitable for wet spinning.
- reconstituted protein fibres typically have relatively low tenacity and high brittleness when compared to protein fibres in their native state, such as silk and wool.
- the process of the present invention can be used to produce a cellulose/protein-containing material. It has not previously been possible achieve a combination of the natural polymers cellulose and protein in a single reconstituted material, for example as a fibre.
- the combination of these two natural polymer materials in a single product may have the potential to go at least some way to overcoming the previously limiting problems of weakness and brittleness in reconstituted protein fibres and/or at least provide the public with a useful choice.
- Another aspect of the present invention relates to a process for producing a cellulose/protein-containing material comprising:
- Another aspect of the present invention relates to a process for producing a cellulose/protein-containing material comprising:
- Another aspect of the present invention relates to a process for producing a cellulose/protein-containing material comprising:
- Preferred protein sources comprise keratin, preferably wool, casein or fibroin, preferably silk.
- the protein source comprises keratin.
- the protein source comprises casein.
- the protein source comprises fibroin.
- Fibrous proteins are generally inert and insoluble in water. Fibrous proteins form long protein filaments shaped like rods or wires. They are structural or storage proteins. Fibrous proteins include keratin and fibroin.
- the protein source comprises keratin.
- Suitable protein sources comprising keratin include, but are not limited to, wool, hair, horns, hooves and feathers.
- the protein source comprises a material such as horns or hooves, the material may be comminuted prior to contact with the solvent.
- the protein source comprises wool, hair, or feathers, or a mixture of any two or more thereof. In another embodiment, the protein source comprises wool or feathers, or a mixture thereof. In a preferred embodiment, the protein source comprises wool, consists essentially of wool, or consists of wool.
- Wool is a keratin protein fibre and is produced by various animals including sheep, goats, camels and rabbits.
- the fibre structure typically comprises a cuticle, cortex, and medulla, although fine wools may lack the medulla.
- the wool is sheep wool.
- the diameter of sheep wool typically ranges from about 10 microns to about 45 microns. Fibre diameter is an important characteristic of wool in relation to its quality and price. Finer wools are softer and suitable for use in garment manufacturing. There are a limited number of consumer applications remaining for stronger wool types such as flooring, bedding, upholstery, and hand knitting yarns.
- the protein source may comprise a mixture of two or more protein sources.
- the protein source may comprise a mixture of two or more of keratin, preferably wool, casein or fibroin, preferably silk.
- a reducing agent is typically added to the solvent.
- a preferred reducing agent is cysteine. Without wishing to be bound by theory, it is thought that cysteine assists with disulfide bond reduction and stabilisation of the zinc formate complex.
- the solvent comprises about 10% w/v to about 70% w/v cysteine. In another embodiment, the solvent comprises about 50% w/v cysteine.
- the cysteine-containing solvent of the invention surprisingly dissolves whole wool up to a concentration of about 30% w/v.
- keratin formate is formed during dissolution, in which the cystine component of the keratin protein is formylated.
- keratin formate may be isolated from a solution in a solvent system comprising cysteine and wool by precipitation, for example by adding water to the solution.
- the resulting keratin formate precipitate may be isolated by filtration and dried.
- the process of the invention comprises:
- a preferred keratin source is wool.
- the dried precipitate which is thought to comprise keratin formate, may be dissolved in formic acid.
- the dried precipitate may also be added to the solution provided by contacting a cellulose source with a solvent comprising zinc ions and formic acid, prior to extrusion and subsequent further process steps.
- protein sources including those comprising casein and fibroin, are also soluble in the solvent of the invention. No reducing agent or cysteine is required for dissolution of these proteins, due to the absence or very low level of cystine in these protein sources.
- the solvent of the invention may dissolve up to about 60% w/v of casein and up to about 20% w/v fibroin.
- the solvent comprising dissolved protein can be contacted with a cellulose source, the solution provided by contacting a protein source with a solvent comprising zinc ions and formic acid being used to dissolve the cellulose.
- the solvent comprising dissolved cellulose can be contacted with a protein source, the solution provided by contacting a cellulose source with a solvent comprising zinc ions and formic acid being used to dissolve the protein.
- a cellulose source and protein source can be simultaneously contacted with a zinc ion/formic acid solvent of the invention to provide a solution.
- the resulting solution comprising both dissolved cellulose and protein can then be extruded and further processed to provide a cellulose/protein-containing material.
- Another aspect of the present invention relates to a process for producing a cellulose/protein-containing material comprising:
- the protein source may be contacted with the solvent simultaneously or sequentially with the cellulose source.
- the protein source may be contacted with the solvent either before or after the cellulose source is contacted with the solvent.
- a preferred protein source comprises keratin, and the solvent then preferably further comprises a reducing agent, preferably cysteine.
- the contacting is typically for a time sufficient to dissolve the protein source.
- the contacting time is about 5 hours to about 8 hours. Contacting times outside this range may, however, still be useful.
- the temperature at which this contacting step is performed may be, for example, up to about 35° C. Temperatures outside this range may, however, still be useful.
- Cellulose formate is a relatively unstable material. Decomposition of the substituents releases formic acid, which can hydrolyse and degrade the regenerated cellulose material. This instability has prevented the widespread use of cellulose formate, despite the extensive use of other cellulose derivatives, such as cellulose acetate.
- the stability of cellulose formate is inversely proportional to the degree of substitution. While a degree of substitution of 2 or 3 (cellulose diformate or cellulose triformate) leads to higher solubility in the solvent of the spinning solution, the resulting extruded fibres are generally unstable, decomposing to release formic acid in the presence of heat leading to fibre degradation.
- the process of the present invention has been found to produce stable cellulose formate material with a degree of substitution of up to about 2. Such materials have further been found to be both sufficiently soluble for spinning and sufficiently stable for practical use as a textile fibre.
- the solution of cellulose or cellulose/protein in the solvent is extruded into a coagulation bath to provide a solid material.
- the solution may be filtered to remove physical impurities and provide a homogeneous solution before extrusion.
- Two or more solutions prepared from the same or different cellulose sources may be combined before extrusion.
- a solution prepared from a cellulose source may be combined with a solution prepared from a protein source prior to extrusion.
- one or more solutions prepared from one or more cellulose sources may be combined with one or more solutions prepared from one or more protein sources prior to extrusion.
- one or more cellulose/protein solutions may be combined, optionally with one or more solutions prepared from one or more cellulose sources and/or one or more solutions prepared from one or more protein sources.
- the solution can be extruded into a coagulation bath in any shape such that the solid material can be formed, for example, as a fibre, film, sheet, coating or particle.
- the solid material is formed as a film by extrusion of the solution through a narrow slit into a coagulation bath.
- the solution is formed into fibres using a conventional wet spinning machine typically used for viscose.
- the solution is typically pumped through a spinneret into a coagulation bath.
- the wet spinning process enables the production of fibres of any desired diameter by selecting the appropriate spinneret.
- the resulting fibres have a consistent diameter and may be produced as single long filaments. This contrasts with naturally occurring fibres, such as wool, which form as staples and for which the diameter is variable and the length limited.
- the fibres may be wound onto a bobbin.
- the extruded fibres may be collected on a take up roller, optionally drawn as required between rollers to improve fibre tensile properties, and then wound onto a bobbin.
- the fibres may also be cut if short staple fibres are required.
- the solid material is formed as a plurality of short fibres by, for example, rapidly forcing the solution through a spinneret into the coagulation bath.
- the coagulation bath typically comprises, consists essentially of or consists of water.
- the invention is not limited thereto.
- the coagulation bath may comprise 1-10% v/v formic acid and/or a soluble formate salt.
- the formate salt may be selected from, for example, lithium formate, sodium formate, potassium formate, calcium formate, copper formate, zinc formate, ammonium formate and mixtures of any two or more thereof.
- the concentration of formate salt in the coagulation bath is between about 20% w/v and about 60% w/v.
- the coagulation bath is typically maintained at a temperature of about 5° C. to about 15° C. Without wishing to be bound by theory, it is thought that extrusion within this temperature range forms the solid material without decomposition of the formate functionality.
- the inventor has surprisingly determined that the resulting solid material can be further stabilised by treatment with an oxidising solution, to subsequently provide the cellulose-containing material or cellulose/protein-containing material.
- the solid material is typically immersed in an oxidising solution.
- a preferred oxidising solution comprises aqueous hydrogen peroxide.
- the invention is not limited thereto and other oxidising solutions, including water comprising a sufficient amount of dissolved oxygen, can be used. For example, water through which air or oxygen has been passed, such that it is saturated with dissolved oxygen.
- the oxidising solution comprises about 0.5% w/w to about 5.0% w/w hydrogen peroxide in water. In another embodiment, the oxidising solution comprises about 0.5% w/w to about 1.0% w/w hydrogen peroxide in water. In another embodiment, the oxidising solution comprises about 0.7% w/w hydrogen peroxide in water.
- a suitable oxidising solution may be prepared by mixing 2% w/v of 35% w/w hydrogen peroxide with water.
- the solid material is immersed in the oxidising solution for about 1 to about 5 minutes. Immersion times outside this range may, however, still be useful.
- the oxidising solution in which the solid material is immersed is frozen.
- the solution may be held in an environment at about ⁇ 20° C. until frozen solid. In one embodiment, the solution is frozen for at least about 2 hours.
- the solid material is then isolated to provide the cellulose-containing material or cellulose/protein-containing material.
- the solid material is isolated by freeze drying to provide the cellulose-containing material or cellulose/protein-containing material.
- the frozen solution is thawed, and the solid material removed from the thawed solution, then dried to provide the cellulose-containing material or cellulose/protein-containing material.
- the frozen solution is thawed at a temperature of about 5° C. to about 30° C. Temperatures outside this range may, however, still be useful.
- the frozen solution may be thawed at ambient (room) temperature, typically about 20° C. to about 25° C.
- the solid material After removal of the solid material from the thawed solution, it may be air dried at ambient (room) temperature, typically about 20° C. to about 25° C., to provide the cellulose-containing material or cellulose/protein-containing material. Preferably, the use of a heat source is avoided during air drying of the solid material.
- the oxidising solution may convert the formate substituents to performate substituents.
- the performate substituents may then rearrange to carbonate and either the performate substituents or carbonate are removed by the subsequent freeze-thaw cycle, or freeze drying.
- the evaporation of the released formic acid during the process of the present invention is thought to stabilise the cellulose-containing material or cellulose/protein-containing material. Otherwise, formic acid would be expected to act on the material with consequential weakening and degradation.
- the solid material may be soaked in water and then frozen, to subsequently provide the cellulose-containing material or cellulose/protein-containing material.
- Another aspect of the present invention relates to a process for producing a cellulose-containing material comprising:
- Another aspect of the present invention relates to a process for producing a cellulose/protein-containing material comprising:
- Another aspect of the present invention relates to a process for producing a cellulose/protein-containing material comprising:
- Another aspect of the present invention relates to a process for producing a cellulose/protein-containing material comprising:
- Another aspect of the present invention relates to a process for producing a cellulose/protein-containing material comprising:
- the solid material is immersed in water for about 1 to about 90 minutes. Immersion times outside this range may, however, still be useful. Preferably, the immersion time is about 30 minutes.
- the solid material is then isolated to provide the cellulose-containing material or cellulose/protein-containing material.
- the solid material is isolated by freeze drying to provide the cellulose-containing material or cellulose/protein-containing material.
- the frozen water is thawed, and the solid material removed from the thawed water, then dried to provide the cellulose-containing material or cellulose/protein-containing material.
- the water is thawed at a temperature of about 5° C. to about 30° C. Temperatures outside this range may, however, still be useful.
- the water may be thawed at ambient (room) temperature, typically about 20° C. to about 25° C.
- the solid material After removal of the solid material from the thawed water, it may be air dried at ambient (room) temperature, typically about 20° C. to about 25° C., to provide the cellulose-containing material or cellulose/protein-containing material. Preferably, the use of a heat source is avoided during air drying of the solid material.
- the solid material may be soaked in an aqueous formate salt solution to subsequently provide the cellulose-containing material or cellulose/protein-containing material.
- the coagulation bath may comprise a soluble formate salt, as described above.
- the aqueous formate salt solution in which the solid material is soaked is typically a different solution.
- the concentration of formate salt in the aqueous formate salt solution is higher than that in the coagulation bath.
- Another aspect of the present invention relates to a process for producing a cellulose-containing material comprising:
- Another aspect of the present invention relates to a process for producing a cellulose/protein-containing material comprising:
- Another aspect of the present invention relates to a process for producing a cellulose/protein-containing material comprising:
- Another aspect of the present invention relates to a process for producing a cellulose/protein-containing material comprising:
- Another aspect of the present invention relates to a process for producing a cellulose/protein-containing material comprising:
- the formate salt is selected from sodium formate, potassium formate, ammonium formate or a mixture of any two or more thereof.
- the aqueous formate salt solution is an aqueous solution of sodium formate.
- the aqueous formate salt solution is an aqueous solution of potassium formate.
- the aqueous formate salt solution is an aqueous solution of ammonium formate.
- the concentration of formate salt in the aqueous formate salt solution is typically between about 20% w/v and about 60% w/v.
- the concentration of formate salt is between about 45% w/v and about 55% w/v. More preferably, the concentration of formate salt is about 50% w/v.
- the solid material is immersed in the aqueous formate salt solution for up to about 16 hours. Shorter or longer immersion times may, however, still be useful. Preferably, the solid material is immersed in the aqueous formate salt solution for up to about 30 to about 90 minutes, more preferably about 60 minutes.
- the solid material After immersion in the aqueous formate salt solution, the solid material is removed from the solution and dried.
- the solid material may be air dried at ambient (room) temperature, typically about 20° C. to about 25° C. or at elevated temperature.
- the solid material is air dried at a temperature of about 45° C.
- the solid material is rinsed in water.
- the solid material may then be air dried at ambient (room) temperature, typically about 20° C. to about 25° C. or at elevated temperature, to provide the cellulose-containing material or cellulose/protein-containing material.
- the solid material is air dried at a temperature of about 45° C.
- the process of the present invention provides a product that can be continuous and have a form or profile controlled by the extrusion process.
- the cellulose source is not continuous and the materials used as the cellulose source typically have a form or profile determined by the growth of a plant. Similar considerations apply to the protein source.
- the process of the invention can be used to produce cellulose/casein fibres that are flexible and fine.
- Another aspect of the present invention relates to a cellulose-containing material or cellulose/protein-containing material produced by a process of the invention.
- Another aspect of the present invention relates to an extruded material comprising cellulose and protein.
- the present invention also relates to a substantially continuous material comprising cellulose and protein.
- the material consists essentially of cellulose and protein. In another embodiment, the material consists of cellulose and protein.
- the material may be a fibre or a film.
- Preferred materials have a protein content of about 5% w/w or more.
- the protein may comprise keratin.
- the keratin is wool keratin.
- the cellulose may be derived from, for example, cotton, wood pulp or plant parts.
- the material may comprise one or more pigments and/or one or more fragrances from the plant parts.
- Another aspect of the invention relates to an extruded material comprising cellulose and one or more pigments and/or one or more fragrances from plant parts.
- Another aspect of the invention relates to a substantially continuous material comprising cellulose and one or more pigments and/or one or more fragrances from plant parts.
- the invention may also be said broadly to consist in the parts, elements and features referred to or indicated in the specification of the application, individually or collectively, in any or all combinations of two or more of said parts, elements or features, and where specific integers are mentioned herein which have known equivalents in the art to which the invention relates, such known equivalents are deemed to be incorporated herein as if individually set forth.
- dehydrated rose flower petals were prepared by drying rose petals following collection. 40 grams of anhydrous zinc formate, prepared as outlined in Part A of Example 1, was dissolved in 100 ml of 98% formic acid. The dehydrated rose flower petals were added to the solution along with 2 grams of wood pulp, a source of cellulose with a high degree of polymerisation, and the mixture stirred for 9 hours to achieve complete dissolution. The resulting solution retained the colour and fragrance of the rose petals.
- Example 1 The solution of Example 1 was transferred into a syringe and pumped using a syringe pump through a spinneret, consisting of 100 holes, each of 100 micron diameter, into a coagulation bath consisting of water at 5-15° C.
- the extruded fibres were collected on a driven take up roller from the coagulation bath and continuously transferred to a bobbin.
- the speed of the take up roller was set to apply a small amount of tension on the extruded fibres to ensure fine, well aligned fibres were formed.
- the bobbin of fibres which were thought to comprise cellulose formate, was soaked in an aqueous solution containing 2% of 35% hydrogen peroxide dissolved in water. Once soaked, the fibres were frozen at ⁇ 20° C. and then freeze dried. Once dry, the fibres (fibres 5A1) were processed as conventional cellulose textile fibres using standard dyeing and textile assembly processes.
- fibres 5A2 were then processed as conventional cellulose textile fibres through standard dyeing and textile assembly processes.
- a bobbin of fibres obtained following the extrusion process described in Example 5A was soaked in water. The fibres were then frozen in the water to form a solid ice block. The ice block was then allowed to thaw at room temperature and the resulting wet fibres allowed to dry at room temperature. Once dry, the fibres (fibres 5B1) were then processed as conventional cellulose textile fibres through standard dyeing and textile assembly processes.
- a bobbin of fibres obtained following the extrusion process described in Example 5A was soaked in an aqueous solution of 50% w/v sodium formate. After soaking for approximately 16 hours, the fibres were then dried at room temperature. After drying, a residue of sodium formate salt was observed on the fibres' surface. The fibres were then rinsed in water and the resulting wet fibres allowed to dry at room temperature. Once dry, the fibres (fibres 5B2) were then processed as conventional cellulose textile fibres through standard dyeing and textile assembly processes.
- Cellulose fibres prepared as described in Example 5B, were analysed using solid state carbon NMR, and compared with the cotton linter used to prepare the cellulose solution in Example 1, Part B. Analysis of the carbon spectrum revealed the presence of a formyl carbonyl carbon in the downfield region of the spectrum (160 ppm) relative to the glucose ring carbons (65-105 ppm), indicating derivatisation of the hydroxyl groups on the cellulose units with formyl groups and the presence of cellulose formate in the fibres.
- the degree of substitution of the cellulose fibres was 1.97 formyl groups per glucose unit (fibres 5B1), 1.67 formyl groups per glucose unit (fibres 5B2) or 1.51 formyl groups per glucose unit (fibres 5C1).
- Example 6 0.5 gram of cotton, a source of native cellulose of a high degree of polymerisation, was added at the same time as the wool to a solution prepared as described in Example 6. The resulting precipitate, thought to be a combination of cellulose formate and keratin formate, was isolated and dried, then dissolved in 98% formic acid. The solution was then used to extrude keratin/cellulose fibres using the methods described in Example 5A. Alternatively, the solution was then used to extrude keratin/cellulose fibres using the methods described in Example 5B.
- the concentration of zinc was halved; 5 grams of anhydrous zinc chloride was added to 20 ml of 98% formic acid. The remaining materials were added as described, specifically 10 grams of cysteine was added and dissolved, followed by 2 grams of clean, dry, crossbred wool and 1 gram of cotton.
- the resulting solution was used to extrude keratin/cellulose fibres using the methods described in Example 5A.
- the solution was used to extrude keratin/cellulose fibres using the methods described in Example 5B.
- the solutions were extruded into keratin/cellulose fibres using the methods described in Example 5A.
- the solution was used to extrude keratin/cellulose fibres using the methods described in Example 5B.
- Example 10 Extrusion of Silk/Cellulose or Casein/Cellulose Fibres
- Example 7 Using the dissolution process described in Example 7, 1 gram of cotton was added to the mixture at the same time as the silk or casein. The resulting solutions, which were thought to contain silk or casein and cellulose formate, were used to extrude silk/cellulose or casein/cellulose fibres using the methods described in Example 5A. Alternatively, the solution was used to extrude keratin/cellulose fibres using the methods described in Example 5B.
- the present invention provides a process for the production of cellulose-containing and cellulose/protein-containing materials.
- the materials can be produced in the form of, for example, fibres or films, the dimensions of which are independent of the dimensions of the cellulose and/or protein source material.
- the materials may be useful in, for example, textiles.
Abstract
Description
-
- (a) contacting a cellulose source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) extruding the solution from (a) into a coagulation bath to provide a solid material;
- (c) immersing the solid material from (b) in an oxidising solution;
- (d) freezing the oxidising solution in which the solid material is immersed; and
- (e) isolating the solid material from (d) to provide the cellulose-containing material.
-
- (a) contacting a cellulose source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) extruding the solution from (a) into a coagulation bath to provide a solid material;
- (c) immersing the solid material from (b) in water;
- (d) freezing the water in which the solid material is immersed; and
- (e) isolating the solid material from (d) to provide the cellulose-containing material.
-
- (a) contacting a cellulose source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) extruding the solution from (a) into a coagulation bath to provide a solid material;
- (c) immersing the solid material from (b) in an aqueous formate salt solution; and
- (d) isolating the solid material from (c) to provide the cellulose-containing material.
-
- (i) adding water to the solution from (a) to provide a precipitate;
- (ii) isolating the precipitate;
- (iii) drying the precipitate; and
- (iv) dissolving the precipitate in formic acid to provide the solution used in (b).
-
- (a) contacting a cellulose source and a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) extruding the solution from (a) into a coagulation bath to provide a solid material;
- (c) immersing the solid material from (b) in an oxidising solution;
- (d) freezing the oxidising solution in which the solid material is immersed; and
- (e) isolating the solid material from (d) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source and a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) extruding the solution from (a) into a coagulation bath to provide a solid material;
- (c) immersing the solid material from (b) in water;
- (d) freezing the water in which the solid material is immersed; and
- (e) isolating the solid material from (d) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source and a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) extruding the solution from (a) into a coagulation bath to provide a solid material;
- (c) immersing the solid material from (b) in an aqueous formate salt solution; and
- (d) isolating the solid material from (c) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) contacting the solution from (a) with a protein source to provide a solution;
- (c) extruding the solution from (b) into a coagulation bath to provide a solid material;
- (d) immersing the solid material from (c) in an oxidising solution;
- (e) freezing the oxidising solution in which the solid material is immersed; and isolating the solid material from (e) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) contacting the solution from (a) with a protein source to provide a solution;
- (c) extruding the solution from (b) into a coagulation bath to provide a solid material;
- (d) immersing the solid material from (c) in water;
- (e) freezing the water in which the solid material is immersed; and isolating the solid material from (e) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) contacting the solution from (a) with a protein source to provide a solution;
- (c) extruding the solution from (b) into a coagulation bath to provide a solid material;
- (d) immersing the solid material from (c) in an aqueous formate salt solution; and
- (e) isolating the solid material from (d) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source and a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) adding water to the solution from (a) to provide a precipitate;
- (c) isolating the precipitate;
- (d) drying the precipitate from (c);
- (e) dissolving the precipitate from (d) in formic acid to provide a solution;
- (f) extruding the solution from (e) into a coagulation bath to provide a solid material;
- (g) immersing the solid material from (f) in an oxidising solution;
- (h) freezing the oxidising solution in which the solid material is immersed; and isolating the solid material from (h) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source and a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) adding water to the solution from (a) to provide a precipitate;
- (c) isolating the precipitate;
- (d) drying the precipitate from (c);
- (e) dissolving the precipitate from (d) in formic acid to provide a solution;
- (f) extruding the solution from (e) into a coagulation bath to provide a solid material;
- (g) immersing the solid material from (f) in an oxidising solution;
- (h) freezing the oxidising solution in which the solid material is immersed; and isolating the solid material from (h) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source and a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) adding water to the solution from (a) to provide a precipitate;
- (c) isolating the precipitate;
- (d) drying the precipitate from (c);
- (e) dissolving the precipitate from (d) in formic acid to provide a solution;
- (f) extruding the solution from (e) into a coagulation bath to provide a solid material;
- (g) immersing the solid material from (f) in an aqueous formate salt solution; and
- (h) isolating the solid material from (g) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) extruding the solution from (a) into a coagulation bath to provide a solid material;
- (c) immersing the solid material from (b) in a treatment liquid;
- (d) optionally freezing the treatment liquid in which the solid material is immersed; and
- (e) isolating the solid material from (c) or (d) to provide the cellulose-containing material.
-
- (a) contacting a cellulose source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) extruding the solution from (a) into a coagulation bath to provide a solid material;
- (c) immersing the solid material from (b) in an oxidising solution;
- (d) freezing the oxidising solution in which the solid material is immersed; and
- (e) isolating the solid material from (d) to provide the cellulose-containing material.
-
- (a) contacting a cellulose source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) contacting the solution from (a) with a protein source to provide a solution;
- (c) extruding the solution from (b) into a coagulation bath to provide a solid material;
- (d) immersing the solid material from (c) in an oxidising solution;
- (e) freezing the oxidising solution in which the solid material is immersed; and isolating the solid material from (e) to provide the cellulose/protein-containing material.
-
- (a) contacting a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) contacting the solution from (a) with a cellulose source to provide a solution;
- (c) extruding the solution from (b) into a coagulation bath to provide a solid material;
- (d) immersing the solid material from (c) in an oxidising solution;
- (e) freezing the oxidising solution in which the solid material is immersed; and isolating the solid material from (e) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source and a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) extruding the solution from (a) into a coagulation bath to provide a solid material; (c) immersing the solid material from (b) in an oxidising solution;
- (d) freezing the oxidising solution in which the solid material is immersed; and
- (e) isolating the solid material from (d) to provide the cellulose/protein-containing material.
-
- (a) contacting a keratin source with a solvent comprising a reducing agent, zinc ions and formic acid to provide a solution;
- (i) adding water to the solution from (a) to provide a precipitate;
- (ii) isolating the precipitate from (i);
- (iii) drying the precipitate from (ii).
-
- (a) contacting a cellulose source and a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) adding water to the solution from (a) to provide a precipitate;
- (c) isolating the precipitate;
- (d) drying the precipitate from (c);
- (e) dissolving the precipitate from (d) in formic acid to provide a solution;
- (f) extruding the solution from (e) into a coagulation bath to provide a solid material;
- (g) immersing the solid material from (f) in an oxidising solution;
- (h) freezing the oxidising solution in which the solid material is immersed; and
- (i) isolating the solid material from (h) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) extruding the solution from (a) into a coagulation bath to provide a solid material;
- (c) immersing the solid material from (b) in water;
- (d) freezing the water in which the solid material is immersed; and
- (e) isolating the solid material from (d) to provide the cellulose-containing material.
-
- (a) contacting a cellulose source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) contacting the solution from (a) with a protein source to provide a solution;
- (c) extruding the solution from (b) into a coagulation bath to provide a solid material;
- (d) immersing the solid material from (c) in water;
- (e) freezing the water in which the solid material is immersed; and
- (f) isolating the solid material from (e) to provide the cellulose/protein-containing material.
-
- (a) contacting a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) contacting the solution from (a) with a cellulose source to provide a solution;
- (c) extruding the solution from (b) into a coagulation bath to provide a solid material;
- (d) immersing the solid material from (c) in water;
- (e) freezing the water in which the solid material is immersed; and
- (f) isolating the solid material from (e) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source and a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) extruding the solution from (a) into a coagulation bath to provide a solid material;
- (c) immersing the solid material from (b) in water;
- (d) freezing the water in which the solid material is immersed; and
- (e) isolating the solid material from (d) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source and a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) adding water to the solution from (a) to provide a precipitate;
- (c) isolating the precipitate;
- (d) drying the precipitate from (c);
- (e) dissolving the precipitate from (d) in formic acid to provide a solution;
- (f) extruding the solution from (e) into a coagulation bath to provide a solid material;
- (g) immersing the solid material from (f) in water;
- (h) freezing the water in which the solid material is immersed; and
- (i) isolating the solid material from (h) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) extruding the solution from (a) into a coagulation bath to provide a solid material;
- (c) immersing the solid material from (b) in an aqueous formate salt solution; and
- (d) isolating the solid material from (c) to provide the cellulose-containing material.
-
- (a) contacting a cellulose source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) contacting the solution from (a) with a protein source to provide a solution;
- (c) extruding the solution from (b) into a coagulation bath to provide a solid material;
- (d) immersing the solid material from (c) in an aqueous formate salt solution; and
- (e) isolating the solid material from (d) to provide the cellulose/protein-containing material.
-
- (a) contacting a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) contacting the solution from (a) with a cellulose source to provide a solution;
- (c) extruding the solution from (b) into a coagulation bath to provide a solid material;
- (d) immersing the solid material from (c) in an aqueous formate salt solution; and
- (e) isolating the solid material from (d) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source and a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) extruding the solution from (a) into a coagulation bath to provide a solid material;
- (c) immersing the solid material from (b) in an aqueous formate salt solution; and
- (d) isolating the solid material from (c) to provide the cellulose/protein-containing material.
-
- (a) contacting a cellulose source and a protein source with a solvent comprising zinc ions and formic acid to provide a solution;
- (b) adding water to the solution from (a) to provide a precipitate;
- (c) isolating the precipitate;
- (d) drying the precipitate from (c);
- (e) dissolving the precipitate from (d) in formic acid to provide a solution;
- (f) extruding the solution from (e) into a coagulation bath to provide a solid material;
- (g) immersing the solid material from (f) in an aqueous formate salt solution; and
- (h) isolating the solid material from (g) to provide the cellulose/protein-containing material.
Claims (19)
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AU2018903502A AU2018903502A0 (en) | 2018-09-18 | Cellulose-containing materials | |
AU2018903502 | 2018-09-18 | ||
PCT/NZ2019/050126 WO2020060419A1 (en) | 2018-09-18 | 2019-09-18 | Cellulose-containing materials |
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US20220080628A1 (en) * | 2020-09-17 | 2022-03-17 | Nutech Ventures | Method of reinforcement for keratin materials |
WO2023000019A1 (en) * | 2021-07-19 | 2023-01-26 | Boulos & Cooper Labs Pty Ltd | Bioplastic and method of making thereof |
Citations (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB190917036A (en) | 1909-07-21 | 1910-07-14 | Nitritfabrik Ag | An Improved Process for Producing Cellulose Formate. |
GB260650A (en) | 1925-06-30 | 1926-11-01 | Fabreik Van Chemische Producte | Manufacture of cellulose formate and of materials therefrom |
US1656119A (en) | 1925-06-04 | 1928-01-10 | Vondelingen Plaat Bv | Method of making and spinning derivatives of cellulose and formic acid |
GB287540A (en) | 1927-03-24 | 1928-11-23 | Vondelingen Plaat Bv | Manufacture of cellulose esters |
GB275641A (en) | 1927-08-04 | 1929-01-04 | Egon Eloed | Process for the production of cellulose esters |
GB690566A (en) | 1950-07-05 | 1953-04-22 | Courtaulds Ltd | Improvements in and relating to the production of regenerated keratin threads, fibres, filaments and the like |
CN85108974A (en) | 1984-04-27 | 1987-05-06 | 米凯林技术研究公司 | The anisotropy composition of cellulose ester prepares the method for said composition and cellulose ester or cellulosic fibre |
US4839113A (en) * | 1984-04-27 | 1989-06-13 | Michelin Recherche Et Technique S.A. | Anistropic compositions of cellulose esters; processes for obtaining such compositions; fibers of cellulose esters or cellulose |
WO2001045917A1 (en) | 1999-12-21 | 2001-06-28 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Tubular films formed from cellulose/protein blends |
US20080241536A1 (en) | 2007-03-29 | 2008-10-02 | Weyerhaeuser Co. | Method for processing cellulose in ionic liquids and fibers therefrom |
US7465321B2 (en) | 2001-08-31 | 2008-12-16 | Keratec Limited | Production of biopolymer film, fibre, foam and adhesive materials from soluble S-sulfonated keratin derivatives |
WO2013043062A1 (en) | 2011-08-19 | 2013-03-28 | Farmcorp Wools Limited | Fibrous protein processing method |
CN103341214A (en) | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin membrane and preparation method thereof |
US20140090640A1 (en) | 2012-09-28 | 2014-04-03 | Industrial Technology Research Institute | Sugar products and fabrication method thereof |
EP2835391A1 (en) | 2013-08-06 | 2015-02-11 | Maxbiogas GmbH | Method for lignin recovery |
CN104764872A (en) | 2015-03-30 | 2015-07-08 | 河北出入境检验检疫局检验检疫技术中心 | Method for identifying lyocell and application of method |
CN104764736A (en) | 2015-03-30 | 2015-07-08 | 河北出入境检验检疫局检验检疫技术中心 | Method for identifying lyocell A100 and application of method |
CN105153316A (en) | 2015-10-19 | 2015-12-16 | 中国科学院青岛生物能源与过程研究所 | Method for preparing nano cellulose by formic acid hydrolysis by using metal salt catalyst |
CN106469762A (en) | 2016-12-01 | 2017-03-01 | 梁结平 | A kind of solar module of anti-PID effect |
CN106867000A (en) | 2017-03-16 | 2017-06-20 | 苏州佰锐生物科技有限公司 | A kind of method for promoting keratolysis and enhancing keratin material intensity |
WO2017155456A1 (en) | 2016-03-11 | 2017-09-14 | Innventia Ab | Method of producing shape-retaining cellulose products, and shape-retaining cellulose products therefrom |
-
2019
- 2019-09-18 US US17/276,089 patent/US11866519B2/en active Active
- 2019-09-18 CN CN201980063087.8A patent/CN112996820A/en active Pending
- 2019-09-18 AU AU2019343086A patent/AU2019343086A1/en active Pending
- 2019-09-18 WO PCT/NZ2019/050126 patent/WO2020060419A1/en unknown
- 2019-09-18 EP EP19863307.5A patent/EP3853263A4/en active Pending
Patent Citations (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB190917036A (en) | 1909-07-21 | 1910-07-14 | Nitritfabrik Ag | An Improved Process for Producing Cellulose Formate. |
US1656119A (en) | 1925-06-04 | 1928-01-10 | Vondelingen Plaat Bv | Method of making and spinning derivatives of cellulose and formic acid |
GB260650A (en) | 1925-06-30 | 1926-11-01 | Fabreik Van Chemische Producte | Manufacture of cellulose formate and of materials therefrom |
GB287540A (en) | 1927-03-24 | 1928-11-23 | Vondelingen Plaat Bv | Manufacture of cellulose esters |
GB275641A (en) | 1927-08-04 | 1929-01-04 | Egon Eloed | Process for the production of cellulose esters |
GB690566A (en) | 1950-07-05 | 1953-04-22 | Courtaulds Ltd | Improvements in and relating to the production of regenerated keratin threads, fibres, filaments and the like |
CN85108974A (en) | 1984-04-27 | 1987-05-06 | 米凯林技术研究公司 | The anisotropy composition of cellulose ester prepares the method for said composition and cellulose ester or cellulosic fibre |
US4839113A (en) * | 1984-04-27 | 1989-06-13 | Michelin Recherche Et Technique S.A. | Anistropic compositions of cellulose esters; processes for obtaining such compositions; fibers of cellulose esters or cellulose |
WO2001045917A1 (en) | 1999-12-21 | 2001-06-28 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Tubular films formed from cellulose/protein blends |
US7465321B2 (en) | 2001-08-31 | 2008-12-16 | Keratec Limited | Production of biopolymer film, fibre, foam and adhesive materials from soluble S-sulfonated keratin derivatives |
US20080241536A1 (en) | 2007-03-29 | 2008-10-02 | Weyerhaeuser Co. | Method for processing cellulose in ionic liquids and fibers therefrom |
WO2013043062A1 (en) | 2011-08-19 | 2013-03-28 | Farmcorp Wools Limited | Fibrous protein processing method |
US20140090640A1 (en) | 2012-09-28 | 2014-04-03 | Industrial Technology Research Institute | Sugar products and fabrication method thereof |
CN103341214A (en) | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin membrane and preparation method thereof |
EP2835391A1 (en) | 2013-08-06 | 2015-02-11 | Maxbiogas GmbH | Method for lignin recovery |
CN104764872A (en) | 2015-03-30 | 2015-07-08 | 河北出入境检验检疫局检验检疫技术中心 | Method for identifying lyocell and application of method |
CN104764736A (en) | 2015-03-30 | 2015-07-08 | 河北出入境检验检疫局检验检疫技术中心 | Method for identifying lyocell A100 and application of method |
CN105153316A (en) | 2015-10-19 | 2015-12-16 | 中国科学院青岛生物能源与过程研究所 | Method for preparing nano cellulose by formic acid hydrolysis by using metal salt catalyst |
WO2017155456A1 (en) | 2016-03-11 | 2017-09-14 | Innventia Ab | Method of producing shape-retaining cellulose products, and shape-retaining cellulose products therefrom |
CN106469762A (en) | 2016-12-01 | 2017-03-01 | 梁结平 | A kind of solar module of anti-PID effect |
CN106867000A (en) | 2017-03-16 | 2017-06-20 | 苏州佰锐生物科技有限公司 | A kind of method for promoting keratolysis and enhancing keratin material intensity |
Non-Patent Citations (8)
Title |
---|
"Polysaccharide-based Fibers and Composites", Lucian Lucia and Ali Ayoub, Editors, published by Springer, chapter 5 pp. 78-117 (Year: 2018). * |
Extended European Search Report for European Application No. 19863307.5 (EESR), dated May 20, 2022, 6 pgs. |
International Search Report and Written Opinion received for PCT Serial No. PCT/NZ2019/050126 dated Oct. 29, 2019, 8 pgs. |
McCall et al., "Chemical Composition of Cotton" Textile Research Journal Jan. 1951, pp. 19-21 (Year: 1951). * |
Office Action dated Mar. 8, 2022 for Chinese Application No. 2019800630878. |
Second Office Action dated Oct. 13, 2022 for Chinese Application No. 201980063087.8, 9 pgs. |
Third Office Action dated Apr. 20, 2023 for Chinese Application No. 201980063087.8, 10 pgs. |
Zeronian et al., "Bleaching of cellulose by hydrogen peroxide" Cellulose vol. 2 pp. 265-272 (Year: 1995). * |
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